The method and the working solution that is used to prepare hydrogen peroxide that prepare hydrogen peroxide
The present invention relates to a kind of method for preparing hydrogen peroxide by the anthraquinone working cycle.Employed working solution contains at least two kinds of 2-alkyl-anthraquinones that replace through difference and/or corresponding 2-alkyl tetrahydro anthraquinone as reaction carriers.The invention still further relates to a kind of new reaction carriers.
In the so-called anthraquinone working cycle that is used for preparing hydrogen peroxide, as the 2-alkyl-anthraquinone of reaction carriers and/or they on nuclear, take place hydrogenant 2-alkyl-α-and/or-the beta-tetrahydro anthraquinone, in the presence of hydrogenation catalyst, in organic solvent system, carry out hydrogenation with hydrogen or the gas that contains hydrogen, and reaction carriers changes into the quinhydrones form at least in part.One or more reaction carriers that are in hydrogenation or oxidised form are commonly called working solution with the described solution that contains organic solvent system.After step of hydrogenation, hydrogenation catalyst is removed from working solution and in oxidation step, working solution is handled with oxygen containing gas, just make the quinone form of reaction carriers again along with the formation of hydrogen peroxide., from through the working solution of oxidation, separating after (water and/or contain the extraction with aqueous solution of hydrogen peroxide) usually come out working solution is added in the step of hydrogenation once more at formed hydrogen peroxide.Except mentioned step, described method also can comprise the regeneration step of working solution, that wherein form and do not have the anthraquinone derivative that reaction carriers renders a service for example the anthraquinone ring oxide compound is re-activated and/or 2-alkyl tetrahydro anthraquinone is changed into corresponding 2-alkyl-anthraquinone derivative by dehydrogenation in working cycle, and as requested, by adding the loss that corresponding 2-substituted anthraquinone and/or tetrahydrochysene derivative have remedied reaction carriers.In order to keep the activity of height, advance a step and be intended to regenerated catalyst.The summary of anthraquinone working cycle is found in the Ullman industrial chemistry encyclopaedia, and the 5th edition, (1989), volume A13,447-457.
For guarantee commerce be installed under the alap inefficacy operate with the high output of most probable and the reaction carriers loss low as much as possible, so reaction carriers is had requirement widely.One of requirement is special in reaction carriers (in the quinone form with in the quinhydrones form) high as far as possible solvability in solvent system.The solvability of quinhydrones form is to available maximum H in the operate continuously process
2O
2Equivalent (the H of every liter of working solution
2O
2The gram number) have a decisive influence.Further require to be relevant to hydrogenation and oxidation kinetics; Two kinds of reactions are to carry out as quickly as possible.Because hydrogenation and oxidation often are the influences of variation that is subjected to the structure of reaction carriers in opposite mode, even also often be a compromise proposal by the sound response carrier system that one or more components are formed.Have great importance equally and be: the chemical stability degree of reaction carriers in catalytic hydrogenation process is high as far as possible, to the high oxidation of oxygen and hydrogen peroxide stability and to the acid in hydrogenation process, used or/and the high stability of alkali.At last, reaction carriers be water miscible as much as possible, nontoxic and manufacturing cost cheap.
According to GB1252822, in the anthraquinone method of preparation hydrogen peroxide, use be the 2-alkyl-anthraquinone, particularly 2-ethyl that have 2-6 carbon atom in one or more the alkyl-, the 2-tertiary butyl-with the 2-amyl anthraquinone.2-alkyl-the tetrahydro-anthraquinone that forms in step of hydrogenation also is effective.
In the above-mentioned English Patent of quoting, do not mention or emphasize in alkyl, to have the 2-alkyl-anthraquinone reaction carriers of 2-6 carbon atom for example.In EP 0286610A and 0778085A, except the 2-alkyl-anthraquinone and their mixture of mentioning other, mentioned that also 2-hexenyl anthraquinone is as reaction carriers.This EP patent documentation is not mentioned the hexenyl isomer which is possible and whether can be reached advantage or reach advantage how.What known is, along with the chain length of alkyl substituent in the 2-alkyl-anthraquinone increases, the quinone solvability increases, but hydrogenation ratio obviously reduces and this has bigger importance in practice simultaneously.As a result, consider use 2-C
6-alkyl-anthraquinone is extremely unconspicuous as reaction carriers.
By JP-A 58180452 and JP-A 59051235 as can be known, 2-(4-methyl-3-pentenyl)-1,4-dihydro-anthraquinone and 2-(4-methyl-3-the pentenyl)-anthraquinone and 2-(4-the methyl amyl)-anthraquinone that can obtain thus can be used as the reaction carriers for preparing hydrogen peroxide.Can find the preparation of described mixture in these documents, raw material is from 1, and 4-naphthoquinones and myrcene make by Diels-Alder reaction.About the use of these compounds in the anthraquinone working cycle that is used for preparing hydrogen peroxide, what only mention is to obtain being same as the result of known 2-alkyl-anthraquinone.
When 2-alkyl-anthraquinone that uses formation in position and/or corresponding alkyl tetrahydro anthraquinone, according to the condition of operation, the requirement of good reaction carriers is only partly satisfied sometimes.Therefore brainstrust is made various effort and is improved reaction carriers by using at least two kinds of different 2-alkyl-anthraquinones and/or their tetrahydrochysene derivative.Yet, be relevant to a kind of or other requirement that reaches by a kind of sound response carrier system and the advantage that produces usually is relevant to the shortcoming of other standard and offsets.
According to DE-AS 1195279, the formation that increases the productive rate of hydrogen peroxide and/or reduce by product in hydrogenation process is possible, if substitute single 2-alkyl-anthraquinone for example the 2-ethyl-, the 2-sec.-propyl-, the 2-sec-butyl-or the 2-tertiary butyl-anthraquinone, and the operating weight ratio is the eutectic mixture of at least two kinds of 2-alkyl-anthraquinones (for example be preferably 2-ethyl-and 2-sec-butyl anthraquinone) of 27: 73, and then the hydrogenant degree remains on below 40%.A shortcoming of this method is that requirement hydrogenant degree must be restricted.One more important disadvantages be the not good hydrogenation kinetics of these eutectic mixtures.Two known from US2966397, as can to exist C in so-called " anthraquinone " system and in " tetrahydro-anthraquinone " system
1-to C
4The similar mixtures of-alkyl-anthraquinone.
A kind of mixture of 2-tertiary butyl anthraquinone and 2-sec.-amyl sec-pentyl secondary amyl anthraquinone is used in the US4374820 suggestion, comprises their tetrahydro-compound.Though this system has good oxidation kinetics, its hydrogenation kinetics is still not good.On the other hand, in German laid-open document DE 1112051 and 1106737 suggestion use a kind of mixture, particularly the 2-sec.-amyl sec-pentyl secondary amyl of isomeric 2-amyl anthraquinone-and a kind of mixture of 2-tert-pentyl anthraquinone and their derivative as reaction carriers.Although because this kind system has good quinone and quinhydrones solvability and can reach high H
2O
2Equivalent, but be still a shortcoming in this not good hydrogenation kinetics, consequently obtain the space-time yield of difference.
Use based on a kind of reaction carriers system of 2-ethyl-anthraquinone (EAQ) and 2-amyl anthraquinone (AAQ) and their tetrahydrochysene derivative (THEAQ and THAAQ) also is known, referring to EP-0453949A and
The chemical economics handbook-SRI international magazine, in June, 1992, CEH product outline hydrogen peroxide.Than reaction carriers system, cause H based on the reaction carriers system of EAQ/THEAQ and AAQ/THAAQ based on 2-ethyl-anthraquinone and 2-ethyl tetrahydro-anthraquinone
2O
2Equivalent increases, and it also can be kept under the cycling condition of operation.Shortcoming of reaction carriers system based on EAQ/THEAQ and AAQ/THAAQ is that it is easy to lose efficacy in step of hydrogenation, and this shows as its hydrogen absorbed dose and lowers.When using for example palladium black of a kind of suspended catalyst, its behavior is feasible must be guaranteed the higher Circulation of hydrogenation catalyst and also further increase it under situation about losing efficacy; Yet the result is that the economical efficiency of this method reduces.
An object of the present invention is to provide the another kind of method of using the working solution contain at least two kinds of 2-alkyl-anthraquinones that replace through difference and/or their tetrahydro-compound to prepare hydrogen peroxide.This method show than use existing known 2-alkyl-anthraquinone binding substances (particularly based on ethyl-and amyl group-anthraquinone and their tetrahydrochysene derivative) method shortcoming still less.In addition, employed reaction carriers system when having good hydrogenation kinetics, causes higher H
2O
2Equivalent, it can be controlled reliably in reaction process and is more difficult inefficacy.
Realized above-mentioned purpose by a kind of method for preparing hydrogen peroxide by the anthraquinone working cycle, described method comprises: step of hydrogenation, the step of oxidation step and separation of hydrogen peroxide, and use and contain at least two kinds through the 2-alkyl-anthraquinone of difference replacement and/or the working solution of their alkyl tetrahydro anthraquinone, the method is characterized in that, employed working solution comprises (I) and is selected from 2-(4-methyl-3-pentenyl)-anthraquinone (IHEAQ), 2-(4-methyl amyl)-anthraquinone (IHAQ), be selected from 2-(C with their at least a reaction carriers among hydrogenant dihydro and tetrahydro-anthraquinone derivative on nuclear with (II)
1-C
5At least a reaction carriers among)-alkyl-anthraquinone and their the tetrahydro-anthraquinone derivative, the content of reaction carriers (I) is 5-95 mole % based on the total amount of all reaction carriers.
In the present invention the component of the reaction carriers of Shi Yonging (I) be selected from 2-(4-methyl-3-pentenyl)-anthraquinone (below be referred to as 2-dissident's thiazolinyl anthraquinone, abbreviate IHEAQ as), 2-(4-methyl amyl)-anthraquinone (below be referred to as the isohexyl anthraquinone, abbreviate IHAQ as), 2-(4-methyl-3-pentenyl)-1,4-dihydro-anthraquinone (=1, the 4-dihydro-IHEAQ), 1,2,3,4-tetrahydrochysene-IHAQ (α-THIHAQ), 5,6,7,8-tetrahydrochysene-IHAQ (β-THIHAQ), 5,6,7,8-tetrahydrochysene-IEHAQ (β-THIHEAQ) and under the condition of anthraquinone process be hydrogenated to the intermediate that THIHEAQ and THIHAQ produce from IHEAQ and IHAQ respectively.In working cycle, β-THIHAQ is mainly made by IHAQ and a spot of α-THIHAQ, the isomeric mixtures that abbreviation THIHAQ representative forms in described technology.Particularly preferred in the methods of the invention reaction carriers (I) is IHEAQ and IHAQ and their beta-tetrahydro derivative, particularly β-THIHAQ.Because the anthraquinone working cycle when IHEAQ is used as the component of reaction carriers (I), after operating for a long time, has formed IHAQ and THIHAQ in working solution.
IHEAQ can be from 1, and 4-naphthoquinones and myrcene be by Diels-Alder reaction, subsequently with air to 1,4 of gained, 4a, 9a-tetrahydrochysene-IHEAQ carries out the oxidation of base catalysis and makes.IHAQ can make by the hydrogenation of for example carrying out IHEAQ on Pt/c.α-THIHAQ can be according to US1425250 by 1, the hydrogenation of 4-dihydro-IHEAQ and making.
The present invention also provides 2-(4-methyl amyl)-5,6,7,8-tetrahydro-anthraquinone (THIHAQ), and it is a kind of reaction carriers that is used for the anthraquinone working cycle of previous the unknown.This compound can be by making with Raney nickel or other hydrogenation catalyst (for example for metallic forms or be bonded to platinum, palladium, rhodium on the carrier) hydrogenation IHEAQ; It also can be made by IHAQ and THIHEAQ in the anthraquinone working cycle.β-THIHEAQ also can be by the Diels-Alder reaction of tetrahydrochysene naphthoquinones and myrcene, and carries out the oxidizing reaction of base catalysis subsequently and make.
As the 2-alkyl-anthraquinone of reaction carriers (II) be selected from the 2-methyl-, the 2-ethyl-, the 2-n-propyl-, the 2-sec.-propyl-, the 2-normal-butyl-, 2-sec-butyl-and the 2-tertiary butyl-and 2-different-sec.-amyl sec-pentyl secondary amyl-and 2-tert-pentyl-anthraquinone and 2-neo-pentyl anthraquinone and/or their tetrahydrochysene derivative.Reaction carriers specifically comprises 2-ethyl-anthraquinone (EAQ) and 2-ethyl-tetrahydro-anthraquinone (α-and β-THEAQ, so far, β-THEAQ is normally main).
According to a preferred embodiment, described working solution mainly comprises a kind of combination of EAQ and IHAQ or IHEAQ and corresponding tetrahydro-compound THEAQ and THIHAQ and/or THIHEAQ as reaction carriers.With reference to described system, will further explain the present invention.
In order to increase H
2O
2It is possible as a kind of working solution of reaction carriers that output, preparation mainly contain EAQ and THEAQ and 2-dissident's thiazolinyl anthraquinone (IHEAQ) or isohexyl anthraquinone (IHAQ) and/or their tetrahydrochysene derivative.Based on the total amount of used active reaction carrier, has the molar weight of the summation (promptly as reaction carriers (I) product) of the anthraquinone derivative and the tetrahydro-anthraquinone derivative of dissident's thiazolinyl and/or isohexyl, normally 5-95%.In the process of preparation, also can be lower than 5% as the molar weight of the product of reaction carriers (I).Used working solution can contain the reaction carriers (I) based on the 10-90 mole % of the total amount of reaction carriers, more preferably contains the reaction carriers (I) of 20-50 mole %.Advantageously, to be adjusted to 10-90 mole % as the molar weight of the anthraquinone derivative of reaction carriers (I), preferred 20-80 mole % and more preferably in the scope of 20-50 mole %, and keep this value then, because the advantageous effects of combination of the present invention, just than immediate reaction carriers system, maximum H
2O
2The growth of output and improved hydrogenation kinetics simultaneously, the reaction carriers that contains EAQ/THEAQ and AAQ/THAAQ obviously is in this scope.
After being added into 2-dissident's thiazolinyl anthraquinone (IHEAQ) in the working solution, dissident's thiazolinyl is hydrogenated to isohexyl in working cycle.Though IHEAQ is not very stable (referring to embodiment 3) to oxidation in essence, is the degraded that dissident's thiazolinyl does not take place in the oxidation step in the anthraquinone working cycle significantly unexpectedly.The content of IHEAQ reduces in working cycle lentamente, and the content of IHAQ and THIHAQ rises simultaneously.The a spot of THIHEAQ that forms when beginning is along with the carrying out of technology is reduced under the limit of detection once more.
According to a preferred embodiment of described method, it is constant that the ratio of the ratio of IHAQ and THIHAQ and EAQ and THEAQ keeps in working cycle basically.Like this, the part of working solution extracts from technology and is added in the dehydrogenation regeneration step of knowing, and wherein existing tetrahydrochysene derivative is formed by dehydrogenation and anthraquinone system again.That part of working solution of regenerated is added in the working cycle once more thus.Advantageously, the 95-5 mole % of all reaction carriers, preferred 60-20 mole % is the anthraquinone form, and the 5-95 mole % of all reaction carriers, preferred 40-80 mole % is the tetrahydro-anthraquinone form.
Find, along with the reaction carriers of type (I) ratio based on all reaction carriers total amounts, that is exactly, and to be IHAQ, IHEAQ and THIHAQ specifically increase anthraquinone solvability and the maximum yields of hydrogen peroxide (H of every liter of working solution based on the ratio of all reaction carriers total amounts
2O
2The gram number) also increased.Its turnout has exceeded the output of the similar system that contains AAQ/THAAQ (substituting IHAQ/THIHAQ), referring to embodiment 4.1-4.13.In addition, described output is along with the ratio of tetrahydro-anthraquinone increases and increases.(existing knowledge is thought in contrast to existing knowledge, hydrogenation kinetics becomes poorer along with the number growth of the carbon atom in the alkyl of reaction carriers), the hydrogenation kinetics of reaction carriers that has the type (I) of isohexyl or dissident's alkenyl group in the present invention is better than the hydrogenation kinetics of isomeric 2-amyl anthraquinone and 2-amyl group-tetrahydro-anthraquinone (AAQ/THAAQ) out of a clear sky, referring to embodiment 5.1-5.6.The reason of the splendid advantage of the inventive method is, uses reaction carriers combination of the present invention, than immediate existing known reaction carriers system (EAQ, AAQ and their tetrahydrochysene derivative), has reached higher H
2O
2Output has been improved hydrogenation kinetics simultaneously.
Reaction carriers system of the present invention can be used for preparing in any method of universal class of hydrogen peroxide.In step of hydrogenation, can use the catalyzer of knowing, for example specifically be, based on the material of precious metal, Pd for example, Pt, Ir, Rh, the mixture of Ru or these precious metals, and Ni, the Raney catalyst of Co or Fe.These catalyzer can be used as suspended catalyst-for example be bonded to palladium black or the precious metal-or be the fixed bed catalyst form on the carrier.Carrier suspends and fixed bed catalyst specifically is at inorganic carrier (SiO for example
2, TiO
2, Al
2O
3, zeolite, BaSO
4, polysiloxane) on precious metal.At last, this catalyzer also can be placed on the surface of layered ceramic carrier or have on the surface of enough honeycomb fashion components on big surface.Special hydrogenation reactor is to be the form of recirculation reactor, fixed-bed reactor, mammoth pump reactor and the reactor with integrated static mixer.
Hydrogenation from room temperature to 100 ℃, is particularly implemented in 45-70 ℃ temperature range usually.Hydrogenation pressure is normally in the scope of about 100kPa to 1Mpa, particularly 200kPa-500kPa.Hydrogenation is so carried out usually so that be introduced into that hydrogen in the step of hydrogenation is used up fully and the hydrogenant degree remains in the scope of 30-80%.
In order to make the reaction carriers component in the solution remain quinone or quinhydrones form, the working solution that contains reaction carriers system of the present invention comprises two or more solvents usually.Suitable solvent or be those used solvents in the existing known anthraquinone working cycle in conjunction with solvent.Except volatile oil aromatic compound (poly-alkylated benzenes), specially suitable solvent compositions also comprises: be selected from for example diisobutyl carbinol(DIBC) of dibasic alcohol, ester, methylcyclohexyl acetate for example, phosphoric acid ester is three (2-ethylhexyl) phosphoric acid ester for example, three-and four-alkyl urea, tetrabutyl urea for example, the ring-type urea, pyrrolidone, carbamate and N-alkyl hexanolactam be one or more solvents of N-hexyl hexanolactam for example.
The major advantage of the inventive method is: than immediate existing known method, to every liter of working solution, H
2O
2The high at least 0.6g/ liter of output; Hydrogenation kinetics improves; The susceptibility that lost efficacy in the operate continuously process is lower; When palladium black was used as catalyzer, the amount of circulation palladium still less.
With reference to the following example and Comparative Examples, the present invention is described in more detail.
Embodiment 1
Preparation 2-(4-methyl-3-pentenyl)-anthraquinone (below be referred to as 2-dissident's thiazolinyl anthraquinone, abbreviate IHEAQ as):
By being similar to JP-A 59-51235, also carry out aromatize subsequently by Diels-Alder reaction, implement this preparation process.
At first used 397g (2.56mol) myrcene (88%, Aldrich) and then add 405g (2.48mol) 1,4-naphthoquinones (97%) is wherein.This suspension is stirred 2 hours (after about 0.5 hour, the thermopositive reaction hexyl is originally finished) down at 100 ℃.Gained reaction mixture (a kind of brown oily liquid) is introduced in the ethanolic soln (3 liters ethanol and 40g sodium hydroxide) of a sodium hydroxide.Suspension was stirred 2 hours down at 50 ℃, and bubbling air-undissolved material at first enters in the solution simultaneously, has the precipitation of reddish yellow to begin to form at last.After cooling, fall solid also with 250 milliliters of ice-cold washing with alcohol by suction filtration.After drying, obtain the 616g yellow powder.The efficient gel liquid-phase chromatographic analysis shows that IHEAQ content is 98.5 surface-area %.1H-NMR spectrogram and fusing point (89-90 ℃, from the normal heptane recrystallize) are corresponding to IHEAQ.
Embodiment 2
Preparation 2-(4-methyl amyl)-beta-tetrahydro anthraquinone (=β-THIHAQ):
To be dissolved in 500 gram (1.7 moles) IHEAQ (raw product) in 3.5 liters the n-butyl acetate at 50 ℃ of hydrogenation reactors that are added to one 5 liters with aerating agitator.With nitrogen wash after the device, 100 gram Raney nickels (being suspended in 500 milliliters of Virahols) added and begin hydrogenization then.Afterwards, the absorption of hydrogen is slowed down suddenly having absorbed 35 liters of hydrogen (quinhydrones formation).After 30 hours, after having absorbed 88 liters of hydrogen, reaction stops.According to high performance liquid chromatography, reaction mixture does not contain catalyzer and solvent, and in the per-cent of surface-area, its contain 33% starting material (=IHEAQ), 45% 2-(4-methyl-3-amyl group)-beta-tetrahydro anthraquinone (=β-THIHEAQ), 11% 2-(4-methyl amyl)-anthraquinone (=IHAQ) and 8% required THIHAQ, in order to remove the alkali cpd of being taken away by employed IHEAQ, respectively with 10% hydrochloric acid, sodium bicarbonate aqueous solution washing and wash the reaction mixture that does not contain catalyzer then with water, and carry out drying then.To in the presence of 100 gram Raney nickels, carry out hydrogenation at n-butyl acetate (3 liters), Virahol (0.5 liter) once more except that 437 remaining after desolvating gram resistatess.After 27.5 hours, when reaction mixture has absorbed 74 liters of hydrogen, reaction terminating.By removing by filter after the catalyzer, make the abundant oxidation of reaction mixture by bubbling air, and concentrate then.Fall throw out and use washed with isopropyl alcohol and last recrystallize by suction filtration.Obtain β-THIHAQ that 304g is a buff powder.According to the efficient gel liquid chromatography, show that IHEAQ content is 98.5 surface-area %.The 1H-NMR spectrogram) corresponding to β-THIHAQ.
Embodiment 3
Measure the oxidative stability of 2-(4-methyl-3-amyl group) anthraquinone (IHEAQ) (=embodiment 3a) than 2-ethyl-anthraquinone (EAQ) (=embodiment 3b):
0.04 mole of quinone IHEAQ or EAQ are dissolved in 100 milliliter 1, in the 2-dichlorobenzene.Added 10 milligrams of Diisopropyl azodicarboxylates as radical initiator after, under the condition that is coated with the oxygen protective layer, stir down with the agitators of aerating at 150 ℃.After 24 hours, by the chromatography determination quinone content.Under the situation of IHEAQ, remaining quinone content is 41%, and is 90% under the situation of EAQ.
Be different from embodiment 3a, under the condition of the anthraquinone working cycle that is used to prepare hydrogen peroxide, IHEAQ does not have oxidative degradation more unexpectedly than EAQ, but in IHEAQ long-time in working cycle is can be detected, because it only is hydrogenated to 2-(4-methyl amyl) anthraquinone (IHAQ) lentamente.
Embodiment 4
The deliquescent mensuration of the quinhydrones of various reaction carriers mixtures in all kinds of SOLVENTS system.Employed reaction carriers and its consumption see Table in 1 and 2.
Method for measuring: will be introduced into by a kind of suspension that relevant work solution and a small amount of new sedimentary palladium black are formed a magnetic stirring, in the thermostatically controlled double-walled container, this container is equipped with a device that is used for the electronics turbidimetry.Use a gas burette, described mixture carries out hydrogenation lentamente.In addition, for fear of reach over-hydrogenation afterwards along with solubility limit, be added into the crystal seed of quinhydrones form.After having write down the fixed turbidity by metering facility, maximum quinhydrones solvability is reached.To become H at the hydroperoxide conversion that this point absorbs
2O
2Equivalent is defined as the H at 20 ℃ of every liter of working solutions
2O
2The gram number.
Embodiment 4.1,4.6,4.8,4.9 and 4.12 right and wrong are according to system of the present invention, and it contains reaction carriers EAQ/THEAQ and AAQ/THAAQ.Embodiments of the invention (4.2-4.5,4.7,4.10,4.11 and 4.13) comprise reaction carriers EAQ/THEAQ and IHAQ/THIHAQ or THEAQ/THIHAQ, wherein: the EAQ=2-EAQ; THEAQ=tetrahydrochysene-2-ethyl-anthraquinone; The AAQ=2-amyl anthraquinone, wherein amyl group represent a kind of 1,2-dimethyl propyl and 1,1-dimethyl propyl (=different-secondary-and tert-pentyl); IHAQ=2-isohexyl anthraquinone; THIHAQ=beta-tetrahydro-IHAQ.In embodiment 4.7, use IHEAQ to replace IHAQ.
Though the hydrogenation temperature in embodiment 4.1 and 4.2 is 60 ℃, other all embodiment implements down at 50 ℃.
In embodiment 4.1 to 4.5, C
9/ C
10-volatile oil aromatic compound (BA) and diisobutyl carbinol(DIBC) (DIBC) are used as solvent with a kind of mixture of 6: 4 volume ratio; In embodiment 4.6 and 4.7, having used volume ratio is 2.5: 1 C
9/ C
10-volatile oil aromatic compound (BA) and tetrabutyl urea (TBU).
In embodiment 4.8 to 4.11, solvent system is by C
9/ C
10-volatile oil aromatic compound (BA) and three (2-ethylhexyl) phosphoric acid ester (TOP) is formed with 3: 1 volume ratio.And it is 2.5: 1 C basically by volume ratio in embodiment 4.12 and 4.13
9/ C
10-volatile oil aromatic compound (BA) and tetrabutyl urea (TBU) are formed.Working solution among the embodiment 4.8 to 4.13 contains the inertia degraded product of employed anthraquinone, because they are in the use of a successive experimental installation midium or long term.The working solution of embodiment 4.12 and 4.13 since their preparation method-used based on EAQ/THEAQ but a kind of operation element solution-it is a kind of than embodiment 4.8 to 4.11 more substantial inert substances.
Table 1
Embodiment number | 4.1 | 4.2 | 4.3 | 4.4 | 4.5 | 4.6 | 4.7 |
The total amount of quinone (mol/l) | 0.70 | 0.70 | 0.70 | 0.70 | 0.70 | 0.70 | 0.70 |
EAQ(mol/l) | 0.14 | 0.14 | 0.17 | 0.09 | 0.11 | 0.22 | 0.22 |
THEAQ (mol/l) | 0.21 | 0.21 | 0.25 | 0.26 | 0.17 | 0.34 | 0.35 |
AAQ (mol/l) | 0.14 | - | - | - | - | 0.06 | - |
THAAQ (mol/l) | 0.21 | - | - | - | - | 0.08 | - |
IHAQ
*) (mol/l)
| - | 0.14 | 0.11 | 0.09 | 0.17 | - | 0.06
**)
|
THIHAQ (mol/l) | - | 0.21 | 0.17 | 0.26 | 0.25 | - | 0.08 |
H
2O
2Equivalent (H
2O
2The gram number/liter)
| 14.3 | 14.8 | 11.9 | 12.4 | 13.0 | 11.7 | 13.7 |
*) employed IHAQ still comprises the IHEAQ of little per-cent
*) use purified IHEAQ to substitute IHAQ
Table 2
Embodiment number | 4.8 | 4.9 | 4.10 | 4.11 | 4.12 | 4.13 |
The total amount of quinone (mol/l) | 0.67 | 0.64 | 0.64 | 0.66 | 0.75 | 0.81 |
EAQ(mol/l) | 0.12 | 0.12 | 0.12 | 0.11 | 0.20 | 0.21 |
THEAQ (mol/l) | 0.29 | 0.26 | 0.29 | 0.28 | 0.38 | 0.41 |
AAQ (mol/l) | 0.13 | 0.09 | - | - | 0.08 | - |
THAAQ (mol/l) | 0.13 | 0.17 | - | - | 0.09 | - |
IHAQ
*) (mol/l)
| - | - | 0.13 | 0.08 | - | 0.10 |
THIHAQ (mol/l) | - | - | 0.11 | 0.19 | - | 0.09 |
H
2O
2Equivalent (H
2O
2The gram number/liter)
| 11.1 | 11.9 | 12.4 | 12.9 | 12.8 | 14.9 |
*) employed IHAQ still comprises the IHEAQ of little per-cent
*) use purified IHEAQ to substitute IHAQ.
From comparative example 4.1 and 4.2,4.6 and 4.7,4.8 and 4.10,4.9 and 4.11 and 4.12 and 4.13 as can be seen, the working solution that contains IHAQ/THIHAQ or IHEAQ/THIHAQ causes obviously higher H than the similar working solution that contains AAQ/THAAQ unexpectedly
2O
2Equivalent.From embodiment 4.3 to 4.5 as can be seen, the mol ratio increase of the anthraquinone total amount that the anthraquinone total amount that replaces along with isohexyl and ethyl replace, H
2O
2Equivalent increases, and described mol ratio increased to H 60: 40 from 40: 60 by 50: 50
2O
2Equivalent reaches 13.0 gram H from 11.9 by 12.4
2O
2/ liter.
Embodiment 5
Studied the hydrogenation kinetics of various working solutions.In table, can obtain H
2O
2Equivalent is 10.0 grams and during 12.0 grams per liters, the used anthraquinone and the composition of solvent and rate constants k (mol minute).
Hydrogenation kinetics standard testing: utilize ultrasonic method that 100 milliliters of working solutions and 30 milligrams of palladium blacks are disperseed and hydrogenation in a double-walled container, being equipped with flow a crusher and an aerating agitator (2000 rev/mins, 50 ℃) and absolute pressure in this double-walled container is the hydrogen of 0.1Mpa.Record hydrogen absorbed dose (Nml) in time.The hydrogenization rate constants k (mol minute) that depends on transformation efficiency is come out from the differential calculation of absorption of hydrogen amount.Hydrogenation kinetics is compared when 0.29 molar yield mutually, corresponding to the H of working solution
2O
2Equivalent is 10.0 gram H
2O
2/ liter, when 0.35 molar yield, compare mutually, corresponding to the H of working solution
2O
2Equivalent is 12.0 gram H
2O
2/ liter.The K value is high more, and hydrogenization is just carried out soon more.
Table 3
Embodiment number | 5.1 | 5.2 | 5.3
*)
| 5.4
*)
| 5.5
**)
| 5.6
**)
|
Solvent | BA/DIBC(60∶40) | BA/top(3∶1) | BA/top(3∶1) |
EAQ (mol/l) | 0.14 | 0.14 | 0.11 | 0.11 | - | - |
THEAQ (mol/l) | 0.21 | 0.21 | 0.26 | 0.29 | 0.21 | 0.21 |
AAQ (mol/l) | 0.14 | - | 0.13 | - | - | - |
THAAQ (mol/l) | 0.21 | - | 0.12 | - | 0.21 | - |
IHAQ (mol/l) | - | 0.14 | - | 0.13 | | |
THIHAQ (mol/l) | - | 0.21 | - | 0.12 | - | 0.21 |
K.10
4In 10.0 gram H
2O
2During/l
| 115 | 121 | 98 | 106 | 310 | 370 |
K.10
4In 12.0 gram H
2O
2During/l
| 86 | 101 | 60 | 75 | 150 | 240 |
*) embodiment 5.3 and 5.4 working solution be taken from and operated some months and also contained a kind of laboratory test device from the inert component of reaction carriers in addition.
*) in test, use than in embodiment 5.1 to 5.4, having more highly active palladium.
Contrast test (5.1,5.3 and 5.5 is not according to the present invention) shows that reaction carriers system of the present invention makes hydrogenization carry out sooner than existing known architectures.EAQ/THEAQ and IHAQ/THIHAQ bonded hydrogenization than EAQ/THEAQ and AAQ/THAAQ bonded hydrogenization (comparing embodiment 5.2 and 5.1) carry out sooner-at H
2O
2Difference became clear especially when equivalent was 12 grams per liters.
Embodiment 6
In the test configurations of the working cycle of the anthraquinone method that is used for preparing hydrogen peroxide, described method is made up of the following step: hydrogenation, oxidation is extracted and dry, regeneration and purifying.To a kind of volatile oil aromatic compound (C by 75 volume %
9/ C
10The mixture of-alkyl-aromatic compounds) and a kind of working solution of forming of three (2-ethylhexyl) phosphoric acid ester of 25 volume %, 0.11 mol 2-ethyl-anthraquinone, 0.29 mol 2-ethyl-tetrahydro-anthraquinone, 0.13 mol 2-isohexyl anthraquinone and 0.12 mol 2-isohexyl tetrahydro-anthraquinone at the maximum H that in operate continuously, obtains
2O
2Output (every liter of H that working solution is produced
2O
2The gram number) studies.Step of hydrogenation (circular form reactor) is to be that 0.35Mpa and temperature are to carry out under 58 ℃ at hydrogen pressure.Use palladium black (0.5~1 grams per liter) as hydrogenation catalyst.H in hydrogenation
2O
2Equivalent is progressively to be increased to 13.0 grams per liters and to keep constant several days, and does not see have quinhydrones to crystallize out.When attempting that output is increased to 13.5 grams per liters, there is quinhydrones to crystallize out.Therefore, the maximum H of working solution
2O
2Output is to be between 13.0 and 13.5 grams per liters.
Embodiment 7 (non-) according to the present invention
Be similar to embodiment 6, measured a kind of maximum H of working solution
2O
2Output.This working solution is by the volatile oil aromatic compound (C of 75 volume %
9/ C
10The mixture of-alkyl-aromatic compounds) and three (2-ethylhexyl) phosphoric acid ester, 0.12 mol 2-ethyl-anthraquinone, 0.28 mol 2-ethyl-tetrahydro-anthraquinone, 0.13 mol 2-amyl anthraquinone and the 0.12 mol 2-amyl group of 25 volume %-tetrahydro-anthraquinone forms.Than embodiment 6,, in this case, need obviously bigger palladium black amount, i.e. 2-3 grams per liter in order under the condition that transforms employed hydrogen fully, to keep hydrogenization.The maximum H of working solution
2O
2Output is to be lower than 12.4 grams per liters.H
2O
2Equivalent increases to the precipitation that just causes quinhydrones more than 12.4.
Embodiment 8
Be similar to embodiment 6, when hydrogenation temperature is 60 ℃, measured a kind of maximum H of working solution
2O
2Output.The solvent system of this working solution is basically based on C
9/ C
10-volatile oil aromatic compound and tetrabutyl urea (volume ratio of BA and TBU is about 3: 1).Described working solution contains 0.20 mol 2-ethyl-anthraquinone, 0.35 mol 2-ethyl tetrahydro-anthraquinone, the 0.09 mol 2-isohexyl anthraquinone (IHAQ) as catalysts, and it also includes a spot of 2-dissident's thiazolinyl anthraquinone (IHEAQ) and 0.07 mol 2-isohexyl-tetrahydro-anthraquinone (THIHAQ).The content of catalyzer is the 0.5-1.0 grams per liter.Maximum H
2O
2Output is 14 gram H at least
2O
2/ liter.Growth is impossible, only is because test configurations does not allow to charge into higher hydrogen.